JPH01215887A - Production of aromatic carboxylic acid - Google Patents
Production of aromatic carboxylic acidInfo
- Publication number
- JPH01215887A JPH01215887A JP3950188A JP3950188A JPH01215887A JP H01215887 A JPH01215887 A JP H01215887A JP 3950188 A JP3950188 A JP 3950188A JP 3950188 A JP3950188 A JP 3950188A JP H01215887 A JPH01215887 A JP H01215887A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- aromatic carboxylic
- oxygen
- carboxylic acids
- naoh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 55
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- -1 aromatic carboxylic acids Chemical class 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 67
- 235000006408 oxalic acid Nutrition 0.000 abstract description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011541 reaction mixture Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IQVLXQGNLCPZCL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 2,6-bis[(2-methylpropan-2-yl)oxycarbonylamino]hexanoate Chemical compound CC(C)(C)OC(=O)NCCCCC(NC(=O)OC(C)(C)C)C(=O)ON1C(=O)CCC1=O IQVLXQGNLCPZCL-UHFFFAOYSA-N 0.000 description 2
- CCFAKBRKTKVJPO-UHFFFAOYSA-N 1-anthroic acid Chemical compound C1=CC=C2C=C3C(C(=O)O)=CC=CC3=CC2=C1 CCFAKBRKTKVJPO-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- SJGINVPFOJFRIV-UHFFFAOYSA-N 2-methylanthracene-1-carboxylic acid Chemical compound C1=CC=CC2=CC3=C(C(O)=O)C(C)=CC=C3C=C21 SJGINVPFOJFRIV-UHFFFAOYSA-N 0.000 description 2
- YOHZZFBEXPAOPC-UHFFFAOYSA-N 2-methylphenanthrene-1-carboxylic acid Chemical compound C1=CC=C2C3=CC=C(C)C(C(O)=O)=C3C=CC2=C1 YOHZZFBEXPAOPC-UHFFFAOYSA-N 0.000 description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 2
- IGPBLYQSLGWUDY-UHFFFAOYSA-N 3-methylnaphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(C(O)=O)C(C)=CC2=C1 IGPBLYQSLGWUDY-UHFFFAOYSA-N 0.000 description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 2
- MMFMTASDTOCTLC-UHFFFAOYSA-N 4-methylbenzene-1,2,3-tricarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O MMFMTASDTOCTLC-UHFFFAOYSA-N 0.000 description 2
- JSBBGWWJLQNXNQ-UHFFFAOYSA-N 4-phenylbenzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC=C1 JSBBGWWJLQNXNQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QNSOHXTZPUMONC-UHFFFAOYSA-N benzene pentacarboxylic acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O QNSOHXTZPUMONC-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- IBFJDBNISOJRCW-UHFFFAOYSA-N 3-methylphthalic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C(O)=O IBFJDBNISOJRCW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
- KVQQRFDIKYXJTJ-UHFFFAOYSA-N naphthalene-1,2,3-tricarboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(C(O)=O)C(C(=O)O)=CC2=C1 KVQQRFDIKYXJTJ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- KFDKNTQGTAEZGC-UHFFFAOYSA-N phenanthrene-1-carboxylic acid Chemical compound C1=CC2=CC=CC=C2C2=C1C(C(=O)O)=CC=C2 KFDKNTQGTAEZGC-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は芳香族カルボン酸類の製造方法に関する。本発
明における芳香族カルボン酸類とは、置換または非置換
の芳香族炭化水素の芳香環に、１個または複数個のカル
ボキシル基が直接結合した化合物あるいはその混合物を
いう。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing aromatic carboxylic acids. The aromatic carboxylic acids in the present invention refer to compounds in which one or more carboxyl groups are directly bonded to the aromatic ring of a substituted or unsubstituted aromatic hydrocarbon, or a mixture thereof.
具体的には、安息香酸、トルイル酸、フタル酸、イソフ
タル酸、テレフタル酸、メチルベンゼンジカルボン酸、
トリメリット酸、ヘミメリット酸、トリメシン酸、メチ
ルベンゼントリカルボン酸、メロファン酸、ピロメリッ
ト酸、ブレニット酸、ベンゼンペンタカルボン酸、ベン
ゼンヘキサカルボン酸の如き置換または非置換のベンゼ
ンカルボン酸類、ビフェニルモノカルボン酸、ビフェニ
ルジカルボン酸、ビフェニルトリカルボン酸の如きビフ
ェニルカルボン酸類、■−ナフトエ酸、２−ナフトエ酸
、ナフタレンジカルボン酸、メチルナフタレンジカルボ
ン酸、ナフタレントリカルボン酸、ナフタレンテトラカ
ルボン酸の如きナフタレンジルボン酸類、フェナントレ
ンモノカルボン酸、メチルフェナントレンモノカルボン
酸、アントラセンモノカルボン酸、メチルアントラセン
モノカルボン酸の如き置換または非置換の二環芳香族カ
ルボン酸類等の各種の化合物あるいはこれらの一部また
は全部の混合物を例示することができる。Specifically, benzoic acid, toluic acid, phthalic acid, isophthalic acid, terephthalic acid, methylbenzenedicarboxylic acid,
Substituted or unsubstituted benzenecarboxylic acids such as trimellitic acid, hemimellitic acid, trimesic acid, methylbenzenetricarboxylic acid, merophanic acid, pyromellitic acid, brennitic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, biphenylmonocarboxylic acid , biphenylcarboxylic acids such as biphenyl dicarboxylic acid and biphenyltricarboxylic acid, ■ naphthalene dicarboxylic acids such as -naphthoic acid, 2-naphthoic acid, naphthalene dicarboxylic acid, methylnaphthalene dicarboxylic acid, naphthalene tricarboxylic acid and naphthalene tetracarboxylic acid, phenanthrene mono Examples include various compounds such as substituted or unsubstituted bicyclic aromatic carboxylic acids such as carboxylic acid, methylphenanthrene monocarboxylic acid, anthracene monocarboxylic acid, and methylanthracene monocarboxylic acid, or mixtures of some or all of these. Can be done.
前記の芳香族カルボン酸類はポリマー、可塑剤、染料等
の合成原料として有用な化合物である。The aromatic carboxylic acids mentioned above are compounds useful as synthetic raw materials for polymers, plasticizers, dyes, and the like.
従来の技術
従来、芳香族カルボン酸類を安価に製造する方法として
石炭の酸化が知られている。すなわち石炭を硝酸酸化、
あるいはアルカリ水溶液中で酸素酸化して各種の芳香族
カルボン酸の混合物として得ている（例えば、有合化、
■、１０９（１９５９）並びにＩｎｄ、 Ｅｎｇ、 Ｃ
ｈｅｗ、 、 ４４．２７８４（１９５２）参照）。BACKGROUND OF THE INVENTION Coal oxidation has been known as a method for producing aromatic carboxylic acids at low cost. In other words, coal is oxidized with nitric acid,
Alternatively, it is obtained as a mixture of various aromatic carboxylic acids by oxygen oxidation in an alkaline aqueous solution (for example, by compounding,
■, 109 (1959) and Ind, Eng, C
Hew, 44.2784 (1952)).
一方、石炭の代りに同様に安価なコールタール−ピッチ
を原料とする方法も検討されており、（１）コールター
ルピッチを水酸化カリウム水溶液中で酸素酸化する方法
（Ｊ、 Ａ＋ｓ、 Ｃｈｅｗ、 Ｓａｃ、 、 Ｅｌｌ
、２３９８（１９３９）参照）や、（２）酸化剤で予備
酸化したのち、アルカリ水溶液中で酸素酸化する方法（
米国特許第２４８１７４０号参照）等が知られている。On the other hand, a method using similarly inexpensive coal tar pitch as a raw material instead of coal is also being considered. , , Ell
, 2398 (1939)) and (2) a method of preliminary oxidation with an oxidizing agent and then oxidation with oxygen in an alkaline aqueous solution (
(see US Pat. No. 2,481,740), etc. are known.
すなわち、（１）ではピッチを１０ｋｇ／ｃ■２の酸素
分圧下、１７ｍｏｌＫ ＯＨ／ｋｇ４２０の水酸化カリ
ウム水溶液中、２５０℃で２４時間反反応せ、シュウ酸
と芳香族カルボン耐類とをそれぞれ６ｗｔ％ならびに３
０ｗｔ％で得ている。また（２）ではピッチを二酸化硫
黄で予備酸化したのち、これを１２．５履ｏ１−ＮａＯ
Ｈ／ｋｇ−Ｈ２Ｏの水酸化ナトリウム中、 ２５０℃で
酸素を導入して全圧を７５０ｐｓｉとし、４時間反応さ
せ、シュウ酸、酢酸、芳香族カルボン酸類の混合物を８
０ｗｔ％で得ている。That is, in (1), pitch was reacted at 250°C for 24 hours in an aqueous potassium hydroxide solution of 17 mol K OH/kg 420 under an oxygen partial pressure of 10 kg/c2, and 6 wt each of oxalic acid and aromatic carboxylic acid were reacted. % and 3
Obtained at 0wt%. In addition, in (2), after pre-oxidizing the pitch with sulfur dioxide, this was
The mixture of oxalic acid, acetic acid, and aromatic carboxylic acids was reacted at 250°C in sodium hydroxide at 250 °C to give a total pressure of 750 psi, and the mixture of oxalic acid, acetic acid, and aromatic carboxylic acids was reacted for 4 hours.
Obtained at 0wt%.
発明が解決しようとする課題
しかし、前記の従来法ではいずれもシュウ酸が多量に副
生ずる。このため石炭を原料とする場合には、酸化条件
が詳細に検討され、シュウ酸の副生を最小限に抑え、か
つ芳香族カルボン酸類の収率を損なわない条件が見つけ
られている。Problems to be Solved by the Invention However, in all of the above conventional methods, a large amount of oxalic acid is produced as a by-product. For this reason, when coal is used as a raw material, oxidation conditions have been studied in detail, and conditions have been found that minimize the by-product of oxalic acid and do not impair the yield of aromatic carboxylic acids.
これに対してコールタールピッチを原料とする場合には
、このような検討は実質上なされていない。また、石炭
とコールタールピッチとは構造がかなり異なるため、石
炭を原料とした場合のシュウ酸副生を最小限にする反応
条件を、コールタールピッチを原料とする場合に適用し
ても、シュウ酸副生を抑制することは出来ない。On the other hand, when coal tar pitch is used as a raw material, such studies are not substantially conducted. Furthermore, since the structures of coal and coal tar pitch are quite different, even if the reaction conditions that minimize oxalic acid by-products when coal is used as a raw material are applied when coal tar pitch is used as a raw material, oxalate It is not possible to suppress acid by-products.
本発明の目的は、コールタールピッチを原料とし、シュ
ウ酸の副生を抑えて経済的に芳香族カルボン酸類を製造
する方法を提供することにある。An object of the present invention is to provide a method for economically producing aromatic carboxylic acids using coal tar pitch as a raw material while suppressing the by-product of oxalic acid.
課題を解決するための手段
本発明は、コールタールピッチを水酸化ナトリウム水溶
液中で酸素ないしは酸素含有ガスで酸化して芳香族カル
ボン酸類を製造するに際し、水酸化ナトリウム水溶液の
濃度が１〜５ ｍｏｌ−Ｎａ［ｌＨ／ｋｇ−Ｈ２Ｏ、反
応温度が２４０〜２８０℃、酸素分圧が２０〜８０ｋｇ
／ｃ１１２の範囲であることを特徴とする芳香族カルボ
ン酸類の製造方法である。Means for Solving the Problems The present invention provides a method for producing aromatic carboxylic acids by oxidizing coal tar pitch in an aqueous sodium hydroxide solution with oxygen or an oxygen-containing gas. -Na[lH/kg-H2O, reaction temperature 240-280℃, oxygen partial pressure 20-80kg
/c112 range.
作用
本発明における水酸化ナトリウム水溶液の濃度は１〜５
ｍｏｌ−ＮａＯＨ／ｋｇ−Ｈ２Ｏの範囲がよい。この
範囲より低い濃度では酸化反応は途中で極端に遅くなる
ため、目的とする芳香族カルボン酸類の収量は低く、経
済的でない。一方、この範囲より高い濃度ではシュウ酸
の副生が著しく、芳香族カルボン酸の収量は却って低下
する。これは以下に示す作用原理に基づくと考えられる
。Effect The concentration of the sodium hydroxide aqueous solution in the present invention is 1 to 5.
A range of mol-NaOH/kg-H2O is preferable. If the concentration is lower than this range, the oxidation reaction becomes extremely slow midway through, resulting in a low yield of the desired aromatic carboxylic acids, which is not economical. On the other hand, if the concentration is higher than this range, the by-product of oxalic acid will be significant, and the yield of aromatic carboxylic acid will actually decrease. This is considered to be based on the principle of operation shown below.
すなわち、本発明の反応ではコールタールピッチが水酸
化ナトリウム触媒により酸化されて、−旦芳香族カルポ
ン酸類が生じ、これが更に水酸化ナトリウム触媒により
酸化分解をうけて、シュウ酸を与えると解される。さて
、コールタールピッチから芳香族カルボン酸類への酸化
段階では、水酸化ナトリウムの触媒作用は比較的小さい
。従って１〜５ ＋＊ｏｌ−ＮａＯＨ／ｋｇ−Ｈ２０と
いう比較的低い濃度でも、反応は支障なく速やかに進行
し、芳香族カルボン酸類が好適に生ずる。That is, in the reaction of the present invention, coal tar pitch is oxidized by a sodium hydroxide catalyst to produce aromatic carboxylic acids, which are further oxidatively decomposed by a sodium hydroxide catalyst to give oxalic acid. . Now, in the oxidation step of coal tar pitch to aromatic carboxylic acids, the catalytic action of sodium hydroxide is relatively small. Therefore, even at a relatively low concentration of 1 to 5+*ol-NaOH/kg-H20, the reaction proceeds quickly without any problem, and aromatic carboxylic acids are suitably produced.
一方芳香族カルポン酸類からシュウ酸への酸化分解は、
水酸化ナトリウムにより著しく促進される。従−） テ
１〜５ ＋＊ｏｌ−ＮａＯＨ／ｋｇ−Ｈ２０の低濃度で
は芳香族カルボン酸類からシュウ酸への酸化分解速度は
小さいが、高濃度例えば１５〜２５ｍｏｌ−ＮａＯＨ／
ｋｇ−Ｈ２０では著しく大きくなり、芳香族カルボン酸
類の収量が低下し、シュウ酸の副生量が顕著に増大する
。On the other hand, the oxidative decomposition of aromatic carboxylic acids to oxalic acid is
Significantly accelerated by sodium hydroxide. Sub-) Te 1 to 5 + * The rate of oxidative decomposition of aromatic carboxylic acids to oxalic acid is low at low concentrations such as 15 to 25 mol-NaOH/kg-H20, but at high concentrations, for example, 15 to 25 mol-NaOH/
kg-H20, the amount increases significantly, the yield of aromatic carboxylic acids decreases, and the amount of oxalic acid by-product increases significantly.
本発明における反応温度は２４０〜２８０℃、好ましく
は２５０〜２７０℃の範囲である。この範囲より低い温
度では反応速度は非常に遅く、実用的でない。一方２８
０℃を超える高温では、シュウ酸の副生、更には最終酸
化生成物である炭酸ガスへの酸化が顕著となり、芳香族
カルボン酸類の収量は低下する。The reaction temperature in the present invention is in the range of 240 to 280°C, preferably 250 to 270°C. At temperatures below this range, the reaction rate is too slow to be practical. On the other hand 28
At high temperatures exceeding 0° C., oxalic acid becomes a by-product and further oxidizes to carbon dioxide, which is the final oxidation product, and the yield of aromatic carboxylic acids decreases.
本発明では酸素ないしは酸素含有ガスで酸化する。酸素
含有ガスとしては、空気、窒素と酸素との混合物、アル
ゴンと酸素との混合物等の反応に関与しない不活性ガス
と酸素との混合物が広範に使用できるが、経済的観点か
らは、空気や窒素と酸素との混合物が好ましい。In the present invention, oxidation is performed using oxygen or an oxygen-containing gas. As the oxygen-containing gas, a wide range of mixtures of oxygen and inert gases that do not participate in the reaction, such as air, mixtures of nitrogen and oxygen, and mixtures of argon and oxygen, can be used. A mixture of nitrogen and oxygen is preferred.
また、酸素の分圧は、２０〜８０ｋｇ／ｃｍ２、好まし
くは３０〜７０ｋｇ／ＣｖＡ２の範囲である。この範囲
内であれば、反応成績の変動は小さく、いずれも本発明
の目的に叶う。Further, the partial pressure of oxygen is in the range of 20 to 80 kg/cm2, preferably 30 to 70 kg/CvA2. Within this range, fluctuations in reaction results are small and the objectives of the present invention are achieved in either case.
本発明の酸化反応では、コールタールピッチ、酸素ない
しは酸素含有ガス、水酸化ナトリウム水溶液の王者の接
触効率が良いと、反応は速やかに進行する。このため本
発明の方法の実施に当っては、前記三巻の混合物をかき
まぜあるいはふりまぜ等の手段によってよく混合するこ
とが好ましい。反応時間は混合状態にも依るが、混合が
充分効率良く行なわれている場合は、通常３時間以内で
あり、これ以上の長時間でも反応成績は大きくは変らな
い。In the oxidation reaction of the present invention, if the contact efficiency among the coal tar pitch, oxygen or oxygen-containing gas, and aqueous sodium hydroxide solution is good, the reaction will proceed rapidly. Therefore, when carrying out the method of the present invention, it is preferable to thoroughly mix the three volumes of the mixture by stirring or shaking. The reaction time depends on the mixing conditions, but if mixing is carried out sufficiently efficiently, it is usually within 3 hours, and reaction results do not change significantly even if the reaction time is longer than this.
このようにして得られた反応混合物から、本発明の目的
とする芳香族カルボン酸類は、例えば次の如くにして単
離できる。すなわち反応混合物を塩酸や硫酸の如き鉱酸
で酸析し、生じた酸類な酢酸エチルやメチルエチルケト
ンの如き有機溶剤で抽出し、抽出液を濃縮して芳香族カ
ルボン酸類を得る。これに少量のシュウ酸が含有される
場合には、減圧留去等の方法で容易に除去することがで
きる。From the reaction mixture thus obtained, the aromatic carboxylic acids targeted by the present invention can be isolated, for example, as follows. That is, the reaction mixture is precipitated with a mineral acid such as hydrochloric acid or sulfuric acid, extracted with the resulting acidic organic solvent such as ethyl acetate or methyl ethyl ketone, and the extract is concentrated to obtain aromatic carboxylic acids. If this contains a small amount of oxalic acid, it can be easily removed by a method such as distillation under reduced pressure.
以下実施例により、本発明を更に詳細に説明する。The present invention will be explained in more detail with reference to Examples below.
実施例
実施例１．３〜１１
ステンレスビーカー中で水酸化ナトリウム２０ｇ（０，
５ｍｏｌ）を水１００ｇに溶かし、５ ｍｏｌ−ＮａＯ
Ｈ／ｋｇ−Ｈ２Ｏの濃度の水酸化ナトリウム水溶液を調
製した。これにコールタールピッチ４ｇを添加し、ビー
カーをかきまぜ機材オートクレーブにはめ込んだ。Examples Examples 1.3-11 In a stainless steel beaker, 20 g of sodium hydroxide (0,
5 mol-NaO) was dissolved in 100 g of water, and 5 mol-NaO
An aqueous sodium hydroxide solution with a concentration of H/kg-H2O was prepared. 4 g of coal tar pitch was added to this, and the beaker was stirred and placed in an equipment autoclave.
オートクレーブ内を窒素置換後雀閉し、かきまぜなから
加熱昇温した。かきまぜ草度は１５００ｒｐ■とした。After replacing the inside of the autoclave with nitrogen, the autoclave was closed, and the temperature was raised while stirring. The stirring rate was set at 1500 rpm■.
所定反応温度まで昇温後、酸素を５０ｋｇ／ｃ■２だけ
圧入し、同温度で所定時間かきまぜた。この間、圧力が
減少した場合には酸素を圧入して全圧が一定に保つよう
にした。室温まで冷却した後常圧に戻し、反応混合物を
水で溶解して全量を２文とし、静置したのち、含有する
生成物を次の方法で分析した。After raising the temperature to a predetermined reaction temperature, oxygen was injected at a rate of 50 kg/cm2, and the mixture was stirred at the same temperature for a predetermined time. During this time, if the pressure decreased, oxygen was pumped in to keep the total pressure constant. After cooling to room temperature, the pressure was returned to normal, and the reaction mixture was dissolved in water to make a total volume of 2. After standing, the product contained was analyzed by the following method.
（１）シュウ酸：上澄液５０−を採取し、６Ｍ塩酸水溶
液を加えて弱酸性にした。煮沸して溶解している二酸化
炭素を除いた後、１Ｍ塩化カルシウム水溶液２０−を加
えて沈殿を析出させた。これに６Ｍアンモニア水３シを
加えて弱アルカリ性とし、６０℃で１時間加温したのち
沈殿を濾別した。(1) Oxalic acid: The supernatant liquid 50- was collected and made weakly acidic by adding 6M hydrochloric acid aqueous solution. After boiling to remove dissolved carbon dioxide, a 1M aqueous calcium chloride solution (20°C) was added to precipitate. Three volumes of 6M ammonia water were added to the mixture to make it slightly alkaline, and after heating at 60°C for 1 hour, the precipitate was separated by filtration.
沈殿を０．１ Ｍアンモニア水で洗浄後、６０〜７０℃
の１０％硫酸水溶液１００−を加えて着色溶液を得た。After washing the precipitate with 0.1 M ammonia water, heat at 60 to 70°C.
A colored solution was obtained by adding 100% of a 10% aqueous sulfuric acid solution.
これを粉末活性炭で脱色処理をした後、含有するシュウ
酸を１／３ＯＮ過マンガン酸カリウム水溶液で滴定した
。After decolorizing this with powdered activated carbon, the oxalic acid contained therein was titrated with a 1/3 ON potassium permanganate aqueous solution.
（２）芳香族カルボン酸類：上澄液５０−を採取し、濃
塩酸を加えて１Ｍ塩酸酸性としたのち２〜３時間加温し
た。析出した沈殿を濾別し、１Ｍ塩酸で濾液が１００−
に達するまで洗節した。得られた濾液を塩化ナトリウム
で飽和させたのち、メチルエチルケトン（ＭＥＫ）１０
０ｄずつで抽出をくり返し、抽出液約２００シを得た。(2) Aromatic carboxylic acids: Supernatant liquid 50- was collected, concentrated hydrochloric acid was added to make it acidic with 1M hydrochloric acid, and then heated for 2 to 3 hours. The deposited precipitate was separated by filtration, and the filtrate was diluted with 1M hydrochloric acid to 100%
It was washed until it reached . After the obtained filtrate was saturated with sodium chloride, 10 ml of methyl ethyl ketone (MEK) was added.
Extraction was repeated at 0 d increments to obtain about 200 d of extract.
これを減圧濃縮し、残留物にＭＥＫＢＯａを加えて不溶
物を濾別した。濾液を減圧濃縮し、残留物を乾燥シリカ
ゲル上で恒温に達するまで３〜７日間減圧乾燥してＭＥ
Ｋ抽出物を得た。これは芳香族カルボン酸類とシュウ酸
との混合物であるので、シュウ酸の量を差し引いたもの
を芳香族カルボン酸類の生成量とした。シュウ酸含有量
は、このＭＥＫ抽出物をメタノールに溶解させて全量を
２５−とし、前記の方法で定量した。表１に結果を示す
。This was concentrated under reduced pressure, MEKBOa was added to the residue, and insoluble materials were filtered off. The filtrate was concentrated under reduced pressure, and the residue was dried under reduced pressure on dry silica gel for 3 to 7 days until reaching constant temperature in ME.
K extract was obtained. Since this is a mixture of aromatic carboxylic acids and oxalic acid, the amount of produced aromatic carboxylic acids was determined by subtracting the amount of oxalic acid. The oxalic acid content was determined by dissolving this MEK extract in methanol to make the total amount 25-, and quantifying it by the method described above. Table 1 shows the results.
実施例２
実施例１において、水酸化ナトリウム２０ｇ（０，５ｍ
ｏｌ）を水５００ｇに溶かして調製した１ ｍｏｌ−Ｎ
ａＯＨ／ｋｇ−Ｈ２Ｏの水酸化ナトリウム水溶液を用い
、他は全く同様の操作を行なった。結果を表１に併記す
る。Example 2 In Example 1, 20 g (0.5 m
1 mol-N prepared by dissolving ol) in 500 g of water
Exactly the same operation was performed except that an aqueous sodium hydroxide solution of aOH/kg-H2O was used. The results are also listed in Table 1.
尚実施例１〜１１で得られた芳香族カルボン酸類はいず
れも各種の化合物の混合物である。この芳香族カルボン
酸を常法によりメチルエステル化してＧＣ−ＭＳで成分
分析を行なった。その結果以下に示す化合物が主に含有
されていることがわかった。Note that the aromatic carboxylic acids obtained in Examples 1 to 11 are all mixtures of various compounds. This aromatic carboxylic acid was methyl esterified by a conventional method, and its components were analyzed by GC-MS. As a result, it was found that the following compounds were mainly contained.
安息香酸、トルイル酸、フタル酸、テレフタル酸、イソ
フタル酸、メチルベンゼンカルボン酸、１−ナフトエ酸
、２−ナフトエ酸、ビフェニルカルボン酸、トリメリッ
ト酸、ヘミメリット酸、トリメシン酸、メチルベンゼン
トリカルボン酸、ビフェニルジカルボン酸、ナフタレン
ジカルボン酸、メチルナフタレンジカルボン酸、ピロメ
リット酸、ブレニット酸、メロファン酸、ビフェニルト
リカルボン酸、フェナンスレンモノカルボン酸、アント
ラセンモノカルボン酸、ナフタレントジカルボン酸、ベ
ンゼンペンタカルボン酸、メチルフェナンスレンモノカ
ルボン酸、メチルアントラセンモノカルボン酸。Benzoic acid, toluic acid, phthalic acid, terephthalic acid, isophthalic acid, methylbenzenecarboxylic acid, 1-naphthoic acid, 2-naphthoic acid, biphenylcarboxylic acid, trimellitic acid, hemimellitic acid, trimesic acid, methylbenzenetricarboxylic acid, Biphenyldicarboxylic acid, naphthalene dicarboxylic acid, methylnaphthalene dicarboxylic acid, pyromellitic acid, brenitic acid, merophane acid, biphenyltricarboxylic acid, phenanthrene monocarboxylic acid, anthracene monocarboxylic acid, naphthalene dicarboxylic acid, benzenepentacarboxylic acid, methyl Phenanthrene monocarboxylic acid, methylanthracene monocarboxylic acid.
実施例１〜１１から明らかなように、本発明の方法を用
いれば、シュウ酸の副生を抑制し、芳香族カルボン酸類
を好適に得ることができる。As is clear from Examples 1 to 11, by using the method of the present invention, the by-product of oxalic acid can be suppressed and aromatic carboxylic acids can be suitably obtained.
（以下余白）
発明の効果
本発明により、安価なコールタールピッチを原料とする
シュウ酸の副生の少ない芳香族カルボン酸類の工業的製
造が可能となった。(The following is a blank space) Effects of the Invention The present invention has made it possible to industrially produce aromatic carboxylic acids with less oxalic acid as a by-product using inexpensive coal tar pitch as a raw material.
代理人弁理士 井 上 雅 生Representative Patent Attorney Masao Inoue
Claims (1)
ないしは酸素含有ガスで酸化して芳香族カルボン酸類を
製造するに際し、氷酸化ナトリウム水溶液の濃度が１〜
５ｍｏｌ−ＮａＯＨ／ｋｇ−Ｈ＿２Ｏ、反応温度が２４
０〜２８０℃、酸素分圧が２０〜８０ｋｇ／ｃｍ＾２の
範囲であることを特徴とする芳香族カルボン酸類の製造
方法。When producing aromatic carboxylic acids by oxidizing coal tar pitch in a sodium hydroxide aqueous solution with oxygen or an oxygen-containing gas, the concentration of the glacial sodium oxide aqueous solution is 1 to 1.
5mol-NaOH/kg-H_2O, reaction temperature is 24
A method for producing aromatic carboxylic acids, characterized in that the temperature is 0 to 280°C and the oxygen partial pressure is in the range of 20 to 80 kg/cm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3950188A JPH01215887A (en) | 1988-02-24 | 1988-02-24 | Production of aromatic carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3950188A JPH01215887A (en) | 1988-02-24 | 1988-02-24 | Production of aromatic carboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01215887A true JPH01215887A (en) | 1989-08-29 |
Family
ID=12554794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3950188A Pending JPH01215887A (en) | 1988-02-24 | 1988-02-24 | Production of aromatic carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01215887A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105683268A (en) * | 2014-01-22 | 2016-06-15 | Lg化学株式会社 | Method for preparing polyaromatic oxide and polyaromatic oxide prepared thereby |
-
1988
- 1988-02-24 JP JP3950188A patent/JPH01215887A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105683268A (en) * | 2014-01-22 | 2016-06-15 | Lg化学株式会社 | Method for preparing polyaromatic oxide and polyaromatic oxide prepared thereby |
| JP2016537451A (en) * | 2014-01-22 | 2016-12-01 | エルジー・ケム・リミテッド | Process for producing polyaromatic oxide and polyaromatic oxide produced thereby |
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